A new fluoroionophore [E-4,4'-di(N-(2-pyridyl)amino)stilbene, E1] with a donor-acceptor-donor framework, which features a central stilbene (acceptor) fluorophore and two terminal pyridylamino (donor) ionophores, is reported. The probe displays an ultrasensitive fluorescence quenching response toward Hg(2+) in H(2)O/THF. Coordination of Hg(2+) to E1 affords a 2:1 complex, enabling the detection of Hg(2+) at a concentration as low as 4.4 × 10(-14) M. The interactions between the two species have been thoroughly characterized with UV-vis absorption spectroscopy, fluorescence spectroscopy, and nuclear magnetic resonance spectroscopy. Density functional theory calculations provide further insights into the nature of the fluorescence quenching response. In contrast, a fluorescent molecule with the donor-acceptor architecture, E-4-(N-(2-pyridyl)amino)stilbene (E4), exhibits a greatly attenuated fluorescence quenching response toward Hg(2+).